Carbon dioxide fixation by an unprecedented hydroxo lead-chromium carbonyl complex: Synthesis, reactivity, and theoretical calculations

Miao Hsing Hsu; Rung Tsang Chen; Wen Shyan Sheu; Minghuey Shieh

doi:10.1021/ic060554o

Carbon dioxide fixation by an unprecedented hydroxo lead-chromium carbonyl complex: Synthesis, reactivity, and theoretical calculations

Miao Hsing Hsu, Rung Tsang Chen, Wen Shyan Sheu, Minghuey Shieh

Department of Chemistry

Research output: Contribution to journal › Article

12 Citations (Scopus)

Abstract

The novel hydroxo-bridged dimeric lead-chromium carbonyl complex [Et ₄N]₂[{PbCr₂(CO)₁₀} ₂(μ-OH)₂] ([Et₄N]₂[1]) was synthesized from the reaction of PbCl₂ and Cr(CO)₆ followed by metathesis with [Et₄N]Br in a KOH/MeOH solution. The X-ray crystallographic structure shows that dianion 1 consists of two Pb{Cr(CO)₅}₂ units bridged by two hydroxo fragments in which the Pb atoms are further coordinated with two Cr(CO)₅ groups, resulting in a distorted tetrahedral geometry. A CO₂ molecule can insert itself into dianion 1 to form two new carbonate complexes, [Et ₄N]₂[{PbCr₂(CO)₁₀}(CO₃)] ([Et₄N]₂[2]) and [Et₄N]₂[{PbCr ₂(CO)₁₀}₂(CO₃)] ([Et ₄N]₂[3]), depending on the reaction conditions. In addition, complex 2 can be transformed into 3 in CH₂Cl₂ solution at an elevated temperature. While the carbonate group in dianion 2 is bonded to one Pb atom, which is coordinated with two Cr(CO)₅ fragments, the carbonate group in 3 bridges the two Pb centers in a μ-1κ²OO′:2κ²OO′ fashion in which each Pb atom is further bonded to two Cr(CO)₅ moieties. Complexes 2 and 3 can be converted back the hydroxo complex 1 under appropriate conditions. All three unprecedented lead-chromium compounds, 1-3, were fully characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The nature and formation of complexes 1-3 were also examined by molecular orbital calculations using the B3LYP method of the density functional theory.

Original language	English
Pages (from-to)	6740-6747
Number of pages	8
Journal	Inorganic Chemistry
Volume	45
Issue number	17
DOIs	https://doi.org/10.1021/ic060554o
Publication status	Published - 2006 Aug 21

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ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Cite this

Hsu, M. H., Chen, R. T., Sheu, W. S., & Shieh, M. (2006). Carbon dioxide fixation by an unprecedented hydroxo lead-chromium carbonyl complex: Synthesis, reactivity, and theoretical calculations. Inorganic Chemistry, 45(17), 6740-6747. https://doi.org/10.1021/ic060554o

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title = "Carbon dioxide fixation by an unprecedented hydroxo lead-chromium carbonyl complex: Synthesis, reactivity, and theoretical calculations",

abstract = "The novel hydroxo-bridged dimeric lead-chromium carbonyl complex [Et 4N]2[{PbCr2(CO)10} 2(μ-OH)2] ([Et4N]2[1]) was synthesized from the reaction of PbCl2 and Cr(CO)6 followed by metathesis with [Et4N]Br in a KOH/MeOH solution. The X-ray crystallographic structure shows that dianion 1 consists of two Pb{Cr(CO)5}2 units bridged by two hydroxo fragments in which the Pb atoms are further coordinated with two Cr(CO)5 groups, resulting in a distorted tetrahedral geometry. A CO2 molecule can insert itself into dianion 1 to form two new carbonate complexes, [Et 4N]2[{PbCr2(CO)10}(CO3)] ([Et4N]2[2]) and [Et4N]2[{PbCr 2(CO)10}2(CO3)] ([Et 4N]2[3]), depending on the reaction conditions. In addition, complex 2 can be transformed into 3 in CH2Cl2 solution at an elevated temperature. While the carbonate group in dianion 2 is bonded to one Pb atom, which is coordinated with two Cr(CO)5 fragments, the carbonate group in 3 bridges the two Pb centers in a μ-1κ2OO′:2κ2OO′ fashion in which each Pb atom is further bonded to two Cr(CO)5 moieties. Complexes 2 and 3 can be converted back the hydroxo complex 1 under appropriate conditions. All three unprecedented lead-chromium compounds, 1-3, were fully characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The nature and formation of complexes 1-3 were also examined by molecular orbital calculations using the B3LYP method of the density functional theory.",

author = "Hsu, {Miao Hsing} and Chen, {Rung Tsang} and Sheu, {Wen Shyan} and Minghuey Shieh",

year = "2006",

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doi = "10.1021/ic060554o",

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T1 - Carbon dioxide fixation by an unprecedented hydroxo lead-chromium carbonyl complex

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AU - Hsu, Miao Hsing

AU - Chen, Rung Tsang

AU - Sheu, Wen Shyan

AU - Shieh, Minghuey

PY - 2006/8/21

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N2 - The novel hydroxo-bridged dimeric lead-chromium carbonyl complex [Et 4N]2[{PbCr2(CO)10} 2(μ-OH)2] ([Et4N]2[1]) was synthesized from the reaction of PbCl2 and Cr(CO)6 followed by metathesis with [Et4N]Br in a KOH/MeOH solution. The X-ray crystallographic structure shows that dianion 1 consists of two Pb{Cr(CO)5}2 units bridged by two hydroxo fragments in which the Pb atoms are further coordinated with two Cr(CO)5 groups, resulting in a distorted tetrahedral geometry. A CO2 molecule can insert itself into dianion 1 to form two new carbonate complexes, [Et 4N]2[{PbCr2(CO)10}(CO3)] ([Et4N]2[2]) and [Et4N]2[{PbCr 2(CO)10}2(CO3)] ([Et 4N]2[3]), depending on the reaction conditions. In addition, complex 2 can be transformed into 3 in CH2Cl2 solution at an elevated temperature. While the carbonate group in dianion 2 is bonded to one Pb atom, which is coordinated with two Cr(CO)5 fragments, the carbonate group in 3 bridges the two Pb centers in a μ-1κ2OO′:2κ2OO′ fashion in which each Pb atom is further bonded to two Cr(CO)5 moieties. Complexes 2 and 3 can be converted back the hydroxo complex 1 under appropriate conditions. All three unprecedented lead-chromium compounds, 1-3, were fully characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The nature and formation of complexes 1-3 were also examined by molecular orbital calculations using the B3LYP method of the density functional theory.

AB - The novel hydroxo-bridged dimeric lead-chromium carbonyl complex [Et 4N]2[{PbCr2(CO)10} 2(μ-OH)2] ([Et4N]2[1]) was synthesized from the reaction of PbCl2 and Cr(CO)6 followed by metathesis with [Et4N]Br in a KOH/MeOH solution. The X-ray crystallographic structure shows that dianion 1 consists of two Pb{Cr(CO)5}2 units bridged by two hydroxo fragments in which the Pb atoms are further coordinated with two Cr(CO)5 groups, resulting in a distorted tetrahedral geometry. A CO2 molecule can insert itself into dianion 1 to form two new carbonate complexes, [Et 4N]2[{PbCr2(CO)10}(CO3)] ([Et4N]2[2]) and [Et4N]2[{PbCr 2(CO)10}2(CO3)] ([Et 4N]2[3]), depending on the reaction conditions. In addition, complex 2 can be transformed into 3 in CH2Cl2 solution at an elevated temperature. While the carbonate group in dianion 2 is bonded to one Pb atom, which is coordinated with two Cr(CO)5 fragments, the carbonate group in 3 bridges the two Pb centers in a μ-1κ2OO′:2κ2OO′ fashion in which each Pb atom is further bonded to two Cr(CO)5 moieties. Complexes 2 and 3 can be converted back the hydroxo complex 1 under appropriate conditions. All three unprecedented lead-chromium compounds, 1-3, were fully characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The nature and formation of complexes 1-3 were also examined by molecular orbital calculations using the B3LYP method of the density functional theory.

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